Method of producing 1,1,1,3,3-pentafluoropropane, a method of producing 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane, and a method of producing 1,1,1,2,3,3-hexachloropropene

ABSTRACT

There are provided production methods of 1,1,1,3,3-pentafluoropropane characterized in that 1,1,1,3,3-pentafluoro-2,3-dichloropropane is reacted with hydrogen fluoride in the presence of a noble metal catalyst; of 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane characterized in that the halogenated propene indicated as general formula I is fluorinated in the presence of antimony trihalogenide and/or antimony pentahalogenide by hydrogen fluoride of mole ratio of or over five times the said antimony halogenide in a liquid phase; and of 1,1,1,2,3,3-hexachloropropene characterized in that 1,1,1,2,2,3,3-heptachloropropane is reacted with an aqueous solution of alkali metal hydroxide in the presence of a phase transfer catalyst. Therefore, an industrial manufacturing method which is possible to obtain the objective product easily at low cost and high yield can be provided.

This is a divisional of application Ser. No. 08/464,834 filed Jun. 27,1995, now U.S. Pat. No. 5,659,093, which is a national stage applicationunder 37 CFR 371 of international application PCT/JP93/01887 filed Dec.24, 1993.

A method of producing 1,1,1,3,3-pentafluoropropane, a method ofproducing 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane, and a methodof producing 1,1,1,2,3,3-hexachloropropene.

Industrial Fields Where the Invention Can Be Utilized

This invention relates to a method of producing1,1,1,3,3-pentafluoropropane which is a useful compound usable as asubstitute for CFC and HCFC which are utilized for a cooling medium, ablowing agent or a cleaning agent and is particularly useful as aurethane blowing agent, besides, a method of producing1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane which can be asynthetic intermediate of 1,1,1,3,3-pentafluoropropane, and a method ofproducing 1,1,1,2,3,3-hexachloropropene.

Prior Art

As a method of preparing 1,1,1,3,3-pentafluoropropane, a reductivereaction with hydrogen wherein 1,2,2-trichloropentafluoropropane is usedas a raw material is known (U.S. Pat. No. 2,942,036).

However, this reaction is not suitable for industrial use due to lowyield and generation of 2-chloropentafluoropropene and1,1,3,3,3-pentafluoropropene which are not reduced enough.

On the other hand, 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane isuseful by itself as an intermediate of medicines or agriculturalchemicals and is a useful compound for the industrial use which can beconducted to hydrofluorocarbon as a substitute for HCFC and CFC whichare used as various cooling mediums, blowing agents or cleaning agents,by fluorination or reduction and which can be conducted to monomers ofvarious kinds of resins by dehydrochlorination. Especially,1,1,1,3,3-pentafluoro-2,3-dichloropropane can be useful as a rawmaterial of 1,1,1,3,3-pentafluoropropane.

Until now, a method of fluorinating propene halogenide with HF in aliquid phase under the presence of a antimony halogenide is known. Forexample, E. T. McBee et al. obtained1,1,1,3,3-pentafluoro-2,3-dichloropropane by fluorinating1,1,1-trifluoro-2,3,3-trichloropropene with HF under the presence ofantimony catalyst (J. Am. Chem. Soc. 70, 2023, (1948)).

However, because 1,1,1-trifluoro-2,3,3-trichloropropene, HF and antimonycatalyst as raw materials are supplied at once to a reactor beforereaction, not only this reaction needs high reaction temperature of 250°C., but also the yield of 1,1,1,3,3-pentafluoro-2,3-dichloropropane isso low as to be 50%, thus this reaction cannot be used industrially.

Besides, 1,1,1,2,3,3-hexachloropropene is useful as an intermediate ofvarious medicines or agricultural chemicals and is a useful raw materialby which an intermediate of various fluorine compounds can besynthesized by fluorinating chlorine of this propene with HF.Especially, it is useful as a raw material of1,1,1,3,3-pentafluoro-2,3-dichloropropane (HCFC 225da).

Generally, 1,1,1,2,3,3-hexachloropropene can be synthesized bydehydrochlorination of 1,1,1,2,2,3,3-heptachloropropane.1,1,1,2,2,3,3-heptachloropropane being a raw material is an economicalindustrial raw material which can be easily synthesized from chloroformand tetrachloroethylene as economical industrial raw materials.

Hitherto, there is known a method of synthesizing1,1,1,2,3,3-hexachloropropene by dehydrochlorination of1,1,1,2,2,3,3-heptachloropropane with alkali metal hydroxide like KOH inalcohol solvent (J. Am. Chem. Soc., 63,1438 (1941)).

However, because of using alcohol as the reaction solvent, this methodneeds to filtrate the alkali metal chloride produced after the reactionand then separate the product from alcohol by the use of the operationsuch as distillation.

And, it is also known that by passing through a reacton tube heatedaround 400° C., it can be obtained from1,1,1,2,2,3,3-heptachloropropane, but this reaction requires hightemperature and use of expensive metal for the material of the reactiontube because of the generation of HCl in the reaction.

Object of the Invention

The first object of this invention is to provide a method being able toproduce 1,1,1,3,3-pentafluoropropane (HFC 245fa) enough in highselectivity in which any problems as mentioned above do not occur.

The second object of this invention is to provide an industrialmanufacturing method which can overcome the above-mentioned problemsincluded in the prior art method of producing1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane and by which1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane (especially, HCFC225da) can be easily produced at low cost and high yield.

The third object of this invention is to solve the problems included inthe above-mentioned prior arts and to provide a method of economicallyproducing 1,1,1,2,3,3-hexachloropropene which can be industrially easilyperformed.

The Constitution of the Invention

As a result of earger study by the inventors regarding a method ofproducing 1,1,1,3,3-pentafluoropropane to solve the above-mentionedproblems, they found that the objective product can be obtained at highyield when a reductive reaction with hydrogen (catalytic reduction) wasperformed by the use of 1,1,1,3,3-pentafluoro-2,3-dichloropropane as araw material under the presence of noble metal catalyst such aspalladium in a gaseous phase, having completed the first invention.

That is, the summary of the first invention is resided in a method ofproducing 1,1,1,3,3-pentafluoropropane at high selectivity of not lessthan 80% by hydrogen reduction reaction using1,1,1,3,3-pentafluoro-2,3-dichloropropane as a raw material, in agaseous phase system in the presence of the noble metal catalyst such aspalladium particularly at the temperature from 30° to 450° C.

In the first invention, it is particularly important that the hydrogenreduction is carried out with the noble metal catalyst in a gaseousphase. For the gaseous phase reaction system of the gaseous phasereaction, a fixed bed-type gaseous phase reaction, a fluidized bed-typegaseous phase reaction and so on can be adopted.

As the noble metal of the noble metal catalyst, palladium and platinumand the like can be nominated and from the point of a selectivity of thereaction, that is, from the point of the small amount of by-productpalladium is preferable. These are desirably carried on at least onekind of carriers selected from active carbon, silica gel, titaniumoxide, zirconia and so on.

Besides, the particle diameter of the carrier does not scarcely affectthe reaction, however, it is desirable 0.1 to 100 mm.

And, the carrying concentration can be applied in wide range from 0.05to 10% (by weight), but it is usually recommended to be from 0.5 to 5%.

The reaction temperature is usually from 30° to 450° C., preferably 70°to 400° C.

In the reductive reaction with hydrogen of1,1,1,3,3-pentafluoro-2,3-dichloropropane, the ratio of hydrogen to theraw material can be varied widely. But usually, at least astoichiometric amount of hydrogen is used for the hydrogenation.Hydrogen of rather more than the stoichiometric amount, for example, 8mole or more 8 mole to the total mole of the starting material can beused.

A reaction pressure is not particularly limited and the reaction can becarried out under pressure, reduced pressure or normal pressure, butpreferable under pressure or normal pressure because the equipment iscomplicated under reduced pressure.

Contact times are usually in the range of 0.1 to 300 seconds,particularly in the range of 1 to 30 seconds.

The raw material, 1,1,1,3,3-pentafluoro-2,3-dichloropropane is a knowncompound and can be obtained by the reaction of fluorinating1,1,1-trifluoro-2,3,3-trichloropropene (E. T. McBEE, ANTHONY TRUCHAN andR. O. BOLT, J. Amer. Chem. Soc., vol 70, 2023-2024 (1948)).

Besides, as a result of earger study by the inventors in relation to amethod of producing 1,1,1,3,3-pentafluoropropane for solving theabove-mentioned problems, they found that the objective product can beobtained at a high yield when a reductive reaction with hydrogen wascarried out by the use of 1,1,1,3,3-pentafluoro-2,3-dichloropropane as araw material in a gaseous phase under the presence of a catalyst inwhich at least one kind of elements selected from zirconium and vanadiumare added to palladium, having completed the second invention.

That is, the summary of the second invention is in a method of producing1,1,1,3,3-pentafluoropropane at high yield of not less than 80% by thereductive reaction with hydrogen particularly at the temperature from30° to 450° C. in a gaseous system by the use of1,1,1,3,3-pentafluoro-2,3-dichloropropane as a raw material in thepresence of a catalyst in which at least one kind of elements selectedfrom zirconium and vanadium are added to palladium.

In the second invention, it is particularly important that the hydrogenreduction reaction is carried out in a gaseous phase system particularlywith the catalyst of palladium added by at least one kind of elementsselected from zirconium and vanadium. For the gaseous phase reactionsystem, a fixed bed-type paseous phase reaction, a fluidized bed-typegaseous phase reaction and so on can be adopted.

The addition amount of zirconium and/or vanadium to palladium is usually0.01 to 4, preferably 0.1 to 2 in the mole retio.

The catalyst to which at least one kind of elements selected fromzirconium and vanadium are added is desirable to be carried on at leastone kind of carriers selected from active carbon, silica gel, titaniumoxide, zirconia and so on.

In this case the above-mentioned metal carried thereon can be in theform of salt and nitrate, oxide salt, oxide, chloride and the like canbe used.

And the particle diameter of the carrier does not scacely affect thereaction, however, it is desirable 0.1 to 100 mm.

As the carrying concentration, it can be used in the wide range from0.05 to 10%, but a product with 0.5 to 5% is usually recommended.

The reaction temperature is usually from 30° to 450° C., preferably 70°to 400° C.

In the reductive reaction with hydrogen of1,1,1,3,3-pentafluoro-2,3-dichloropropane, the ratio of hydrogen to theraw material can be varied widely. But usually, at least astoichiometric amount of hydrogen is used for the hydrogenation.Hydrogen of rather more than the stoichiometric amount, for example, 8mole or more 8 mole to the total mole of the starting material can beused.

A reaction pressure is not particularly limited and the reaction can becarried out under pressure, reduced pressure or normal pressure, butpreferable under pressure or normal pressure because the equipment iscomplicated under reduced pressure.

Contact times are usually in the range of 0.1 to 300 seconds,particularly in the range of 1 to 30 senconds.

Besides, to solve the above-mentioned problem, the inventors found amethod of producing 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane(for example, 1,1,1,3,3-pentafluoro-2,3-dichloropropane) characteried byfluorinating propene halogenide indicated as ##STR1##

(provided that in this general formula, X and Y are Cl or Frespectively.)

(for example, 1,1,1,2,3,3-hexachloropropene) with hydrogen fluoride inthe presence of antimony trihalogenide and/or antimony pentahalogenidein a liquid phase, wherein the hydrogen fluoride of mole ratio of orover five times antimony trihalogenide and/or antimony pentahalogenideis present in the reaction system, so that they have reached the thirdinvention.

The third invention is, for example, to produce1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane by fluorinating propenehalogenide of the above-mentioned general formula I in the coexistenceof fluorinated-chlorinated antimony being antimony trihalogenide and HF.

In the third invention, it is known that antimony chloride added to thereaction system is partially fluorinated into SbClxFy (x+y=5) in thepresence of HF, and the inventors found that in the case of using it ascatalyst for the fluorination of compound having hydrogen or double bondcapable of being chlorinated such as halogenated propene, the more thefluorine content, the more quickly the reaction of fluorinating iscarried out to inhibit the formation of chlorinated product being aby-product of the reaction.

There was found that by coexistence of HF which is excessive in amountto the added antimony trihalogenide and/or antimony penta halogenide,the fluorine content of antimony trihalogenide and/or antimonypentahalogenide can be kept high and the addition reaction can bepromoted to synthesize 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropaneat high selectivity, having completed the third invention.

The amount of HF supplied into a reactor consists of a consumptionamount of HF added by the lost amount accompanied with the product. Thatis, the amount of HF in the reaction system is thus kept constant.However, the variation of the range permissible in the capacity of thereactor is allowed if the excess rate of HF can be maintained. Besides,all of the required amount of HF can be also charged into the reactorbefore the reaction.

The introduction amount per an hour (supply rate) of halogenated propenecharged into the reactor must be lesser to fluorinated-chlorinatedantimony added to the system, but the lesser amount is not desirable dueto decrease of the production amount per the capacity of the reactor.

But if the amount is so large, fluorine content offluorinated-chlorinated antimony decreases so that the selectivity islowered although the reaction proceeds. That is, the introduction amountof propene halogenide to the charged fluorinated-chlorinated antimony isusually set not more than 100 times mole/Hr and not less than 2 timesmole/Hr. It is desirable to be set not more than 50 times mole/Hr andnot less than 5 times mole/Hr.

The reaction advances whenever the reaction temperature is 40° C. orover, but in this case, if the supply amount of propene halogenide tothe charged fluorinated-chlorinated antimony is lesser, the selectivitydecreases.

A high reaction temperature is favorable in points of the productivityand the selectivity, but a reaction pressure should be kept highaccording to the reaction temperature. Because keeping the reactionpressure high raises the cost of equipment, the reaction is practicallydesirable to be carried out in the range from 50° to 150° C.

Besides, the reaction pressure is elevated according to the reactiontemperature, and an adequate value can be selected in the range from 3kg/cm³ to 30 kg/cm³ in order to separate HF and the product. And, theobject can be obtained at high yield with keeping reaction pressureconstant, by slowly supplying propene halogenide as a raw material andhydrogen fluoride into the reaction system and by selecting the produced1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane.

Increase in amount of HF coexisted with fluorinated-chlorinated antimonyin the reaction system does not affect the selectivity of the reaction,but it lowers the productivity per reactor capacity. In the case of thesmall amount, although the reaction advances, the supply amount ofpropene halogenide must be small owing to avoid the decrease of theselectivity. In practice, the reaction should be carried out in whichthe amount of hydrogen fluoride to fluorinated-chlorinated antimony isfive times or more mole of the latter, preferably not more than fivehundreds times. More desirably, HF of fifty times or over and twohundreds times or less moles is coexisted.

Still more, in addition to the above described ones, antimonytrihalogenide and antimony pentahalogenide usable in the third inventionare a mixture of SbF₃ and SbCl₅, SbF₃ with SbCl₂ F₃ as a part convertedby Cl₂ therefrom and so on.

Further, as a result of eager study by the inventors to solve theabove-mentioned problems, they found that in a reaction ofdehydrochlorinating of heptachloropropane, it advances under a moderatereaction condition by reacting 1,1,1,2,2,3,3-heptachloropropane with anaqueous solution of alkali metal hydroxide in the presence of a suitablephase transfer catalyst, having completed the fourth invention.

That is, the fourth invention is concerned to a method of producing1,1,1,2,3,3-hexachloropropene characterized in that1,1,1,2,2,3,3-heptachloropropane is reacted with an aqueous solution ofthe alkali metal hydroxide in the presence of the phase transfercatalyst.

In general, an ionic compound like the alkali metal hydroxide is notsoluble in heptachloropropane. Therefore, the reaction is generallycarried out using a compatible solvent like alcohol. However, thismethod needs to separate the used reaction solvent from the producedobject after the reaction. Besides, it might be considered to performthe reaction using an aqueous solution of alkali metal hydroxide intwo-phase system, but the reaction is generally so slow that it oftenneeds violent conditions in two-phase system.

However, there was found that when according to the fourth invention thereaction is carried out using the aqueous solution of alkali metalhydroxide in two-phase system under the presence of the phase transfercatalyst, particularly below-mentioned tetraalkylammonium salt ortetraalkyl phosphonium salt, it proceeds quickly in a mild condition.

For cation of tetraalkyl ammonium salt used in the reaction,benzyltriethyl ammonium, trioctylmethyl ammonium, tricaprylmethylammonium, and tetrabutyl ammonium etc. can be given.

And, for cation of tetraalkyl phosphonium salt, tetrabutyl phosphoniumand trioctylethyl phosphonium etc. can be given.

The anion constituting the salt with the above-mentioned cation is notlimited, but chloride ion and hydrogensulfate ion etc. can be cited ingeneral.

However, the above-mentioned ones are nothing but examples and does notrestrict the kind of a catalyst.

Besides, for alkali metal hydroxide usable in the above-mentionedreaction, NaOH, KOH and so on can be exemplified. The concentration ofthe aqueous solution of this alkali metal hydroxide is not limited,however, it may be from 5 to 50%, preferably from 20 to 40% for thereaction.

These aqueous solutions can be reused after removing the produced alkalimetal chloride by way of precipitation, filtration or the like andadding the alkali metal hydroxide again.

The reaction is carried out in two-phase system to generate phaseseparation easily so as to obtain an objective crude product of1,1,1,2,3,3-hexachloropropene. The obtained crude product can be easilyrefined by distillation and the used catalyst and the unreactedheptachloropropane can be recovered.

The reaction is usually carried out at a temperature from the roomtemperature to 80° C., desirably from 40° to 60° C.

And, 1,1,1,2,2,3,3-heptachloropropane as a raw material can be obtainedby reacting tetrachloroethylene with chloroform in the presence of aLewis acid catalyst like alminium chloride (See Patent Opening No.118333/1986 etc.).

Concerning from the first invention to the fourth invention asabove-mentioned, the products obtained by the production method of eachinvention are usable as follows:

First 1,1,1,2,3,3-hexachloropropene as a raw material which is obtainedby the production method of the fourth invention can be led to1,1,1,3,3-pentafluoro-2,3-dichloropropane by the production method ofthe third invention, then this can be led to1,1,1,3,3-pentafluoropropane by the production method of the first orthe second invention. The object can be obtained at high yield throughthis series of process from a cheap raw material easily available, whichis superior in economy.

In this case, 1,1,1,2,3,3-hexachloropropene obtained by the productionmethod of the fourth invention can be led to1,1,1,3,3-pentafluoro-2,3-dichloropropane by the production method ofthe third invention, then this can be taken out as a product. In thisprocess, there is given an advantage that the obtained product can beused as an intermediate of medicines or agricultural chemicals or anintermediate of monomer of resins.

And, 1,1,1,3,3-pentafluoro-2,3-dichloropropane as a raw materialobtained by the production method of the third invention can be led to1,1,1,3,3-pentafluoropropane by the production method of the first orsecond invention. This series of process brings about an advantage that1,1,1,3,3-pentafluoropropane which is important for a urethane blowingagent can be produced at high yield.

The Possibility of Utilizing the Invention in Industry

Because in the first and second inventions the reductive reaction withhydrogen in which the raw material is1,1,1,3,3-pentafluoro-2,3-dichloropropane is carried out in the presenceof the noble metal catalyst like pallasium catalyst particularly at thetemperature from 30° to 450° C., 1,1,1,3,3-pentafluoropropane can beproduced at high selectivity of 80% or over.

And, the third invention can offer an industrial production methodcapable of manufacturing1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane at low cost and highyield and easily because propene halogenide indicated as general formulaI is fluorinated with hydrogen fluoride of mole ratio of five times ormore antimony halogenide under the presence of antimony trihalogenideand/or antimony petahalogenide in a liquid phase.

Besides, in the fourth invention, 1,1,1,2,3,3-hexachloropropene can beproduced at low cost in a manner that can be industrially and easilyperformed because of reacting 1,1,1,2,2,3,3-heptachloropropane with theaqueous solution of alkali metal hydroxide under the presence of thephase transfer catalyst.

Embodiments

Hereafter, examples of this invention will be variously explained,however, those can be variously modified on the basis of the technicalconcept of this invention.

EXAMPLE 1

20 cc of a palladium catalyst carried on active carbon in 0.5%concentration was filled in a SUS316-made reaction tube having insidediameter of 2 cm and length of 40 cm and heated to 250° C. by anelectric furnace under nitrogen flow. After reaching a giventemperature, the nitrogen gas was replaced with hydrogen gas and thishydrogen gas was flowed for a time.

Next, beforehand gasified 1,1,1,3,3-pentafluoro-2,3-dichloropropane andhydrogen gas were introduced into the reaction tube respectively at 16.7cc/min and 140 cc/min. The reaction temperature was kept at 250° C.

Produced gases were analyzed by gas chromatography after washed withwater and dried by calcium chloride. The result is shown in table-1.

EXAMPLE 2

A reaction was carried out under the same condition as that of Example 1except flow rates of hydrogen gas and1,1,1,3,3-pentafluoro-2,3-dichloropropane were respectively at 140cc/min and 17 cc/min, and the reaction temperature was 270° C. Theresult is shown in table-1.

                  TABLE 1                                                         ______________________________________                                        example    conversion ratio (%)                                                                       selectivity (%)                                       ______________________________________                                        1          100          91                                                    2          100          89                                                    ______________________________________                                    

According to these results, the objective compound can be obtained atconversion ratio of 100% and high selectivity of not less than 80% bythe reaction based on the first invention.

EXAMPLE 3

20 cc of a catalyst in which palladium and zirconium were carried onactive carbon respectively in concentration of 0.5% and 0.25% was filledin a SUS316-made reaction tube having inside diameter of 2 cm and lengthof 40 cm and heated to 250° C. by an electric furnace under nitrogenflow. After reaching a predetermined temperature, the nitrogen gas wasreplaced with hydrogen gas and this hydrogen gas was flowed for a time.

Next, beforehand gasified 1,1,1,3,3-pentafluoro-2,3-dichloropropane andhydrogen gas were introduced into the reaction tube respectively at 16.7cc/min and 140 cc/min. The reaction temperature was kept at 250° C.

Produced gases were analyzed by gas chromatography after washed withwater and dried by calcium chloride. The result is shown in table-2.

EXAMPLE 4

A reaction was carried out under the same condition as that of Example 3except the flow rates of hydrogen gas and1,1,1,3,3-pentafluoro-2,3-dichloropropane were changed respectively to120 cc/min and 35 cc/min. The result is shown in table-2.

EXAMPLE 5

20 cc of a catalyst wherein palladium and vanadium were carried onactive carbon respectively in concentration of 0.5% and 0.25% was filledin a SUS316-made reaction tube having inside diameter of 2 cm and lengthof 40 cm and heated to 250° C. by an electric furnace under nitrogenflow. After reaching a given temperature, the nitrogen gas was changedwith hydrogen gas and this hydrogen gas was flowed for a time.

Next, beforehand gasified 1,1,1,3,3-pentafluoro-2,3-dichloropropane andhydrogen gas were introduced into the reaction tube respectively at 16.7cc/min and 140 cc/min. The reaction temperature was kept at 250° C.

Produced gases were analyzed by gas chromatography after washed withwater and dried by calcium chloride. The result is shown in table-2.

EXAMPLE 6

A reaction was carried out under the same condition as that of Example 5except changing of the flow rates of hydrogen gas and1,1,1,3,3-pentafluoro-2,3-dichloropropane respectively to 280 cc/min and32 cc/min. The result is shown in table-2.

                  TABLE 2                                                         ______________________________________                                        example    conversion ratio (%)                                                                       selectivity (%)                                       ______________________________________                                        3          100          92                                                    4          100          89                                                    5          100          92                                                    6          100          88                                                    ______________________________________                                    

According to these results, the objective compound can be obtained atconversion ratio of 100% and high selectivity of not less than 80% bythe reaction based on the second invention.

EXAMPLE 7

29.9 g (0.1 mol) of SbCl₅ was charged into a Hastelloy-made autoclave of500 ml with a condenser and after cooling it 300 g (15 mol) of HF wasadded thereto. Then, the temperature was slowly raised and the reactionwas carried out at 80° C. for 3 hours.

1,1,1,2,3,3-hexachloropropene and HF were added respectively at 0.2mol/Hr and 1.2 mol/Hr with keeping the temperature at 80° C. A reactionpressure was controlled in the range from 9 kg/cm³ to 11 kg/cm³ so thatweight of the reactor become constant.

During the reaction, hydrogen chloride and product produced were takenout of an upper portion of the condenser, then the product was capturedwith a dry ice trap after hydrogen chloride was washed with water. Onadding 249 g (1 mol) of 1,1,1,2,3,3-hexachloropropene, the reaction wasstopped.

After the reaction, the pressure was slowly decreased and the contentwas selected out. As a product, 190 g of organic substance was obtained.

It was confirmed with GLC (gas-liquid chromatography) that 97% of theproduct was the objective 1,1,1,3,3-pentafluoro-2,3-dichloropropane (91%of the yield). A main by-product was1,1,1,3-tetrafluoro-2,3,3-trichloropropane being a reaction intermediateand halogenated propane to which chlorine was added was not detected.

EXAMPLE 8

29.9 g (0.1 mol) of SbCl₅ was charged into a Hastelloy-made autoclave of500 ml with a condenser and after cooling it 300 g (15 mol) of HF wasadded thereto. Then, the temperature was slowly raised and the reactionwas carried out at 80° C. for 3 hours.

1,1,1,2-tetrafluoro-3,3-dichloropropene and HF were added respectivelyat 0.2 mol/Hr and 0.6 mol/Hr with keeping the temperature at 80° C. Areaction pressure was controlled in the range from 9 kg/cm³ to 11kg/cm³.

In the reaction, hydrogen chloride and product produced were selectedout of an upper portion of the condenser, then the product was collectedwith a dry ice trap after hydrogen chloride was washed with water. Onadding 183 g (1 mol) of 1,1,1,2-tetrafluoro-3,3-dichloropropene, thereaction was stopped.

After the reaction, the pressure was slowly decreased and the contentwas selected out. As a product, 177 g of organic substance was obtained.

It was confirmed with GLC that 98.5% of the product was the objective1,1,1,2,3,3-hexafluroro-3-chloropropane (94% of the yield).

A main by-product was 1,1,1,2,3-pentafluoro-3,3-dichloropropane being areaction intermediate and halogenated propane to which chlorine wasadded was not detected.

EXAMPLE 9

29.9 g (0.1 mol) of SbCl₅ was supplied to a Hastelloy-made autoclave of500 ml with a condenser and after cooling it 300 g (15 mol) of HF wasadded thereto. Then, the temperature was slowly raised and the reactionwas carried out at 80° C. for 3 hours.

1,1,1-trifluoro-2,3,3-trichloropropene and HF were added respectively at0.2 mol/Hr and 0.8 mol/Hr with keeping the temperature at 80° C. Areaction pressure was controlled in the range from 10 kg/cm³ to 12kg/cm³.

In the reaction, hydrogen chloride and product produced were selectedout of an upper portion of the condenser, then the product was capturedwith a dry ice trap after hydrogen chloride was washed with water. Onadding 199 g (1 mol) of 1,1,1-trifluoro-2,3,3-trichloropropene, thereaction was stopped.

After the reaction, the pressure was slowly decreased the content wasselected out. As a product, 198 g of organic substance was obtained.

It was confirmed with GLC that 98% of the product was the objective1,1,1,3,3-pentafluroro-2,3-dichloropropane (96% of the yield).

A main by-product was 1,1,1,3-tetrafluoro-2,3,3-trichloropropane being areaction intermediate and halogenated propane to which chlorine wasadded was not detected.

EXAMPLE 10

A reaction was carried out under the same condition as that of Example 7except charging 29.9 g (0.1 mol) of SbCl₅ and 17.9 g (0.1 mol) of SbF₃in a Hastelloy-made autoclave of 500 ml with a condenser.

as a product, 196 g of organic substance was obtained. It was confirmedwith GLC that 98% of the product was the objective1,1,1,3,3-pentafluroro-2,3-dichloropropane (94% of the yield). A mainby-product was 1,1,1-tetrafluoro-2,3,3-trichloropropane and a compoundwith added chlorine was not detected.

According to the above-mentioned results, by the reaction based on thethird invention 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane can beproduced easily at high yield.

EXAMPLE 11

285.5 g (1.0 mol) of 1,1,1,2,2,3,3-heptachloropropane and 0.3 g (0.1mmol) of tetrabutyl ammonium chloride were charged into a round bottomflask of 500 ml with a Dimroth condenser and a dropping funnel.

With keeping it at 40° C. and agitating violently, 250 ml of KOH aqueoussolution of 20% concentration was dropped for 1 hour. After the droppingwas finished, the agitating was stopped and an organic layer or a lowerlayer was analyzed. 1,1,1,2,2,3,3-heptachloropropane as a raw materialdisappeared and the organic layer consisted of only1,1,1,2,3,3-hexachloropropene.

The reaction solution was transferred to a separatory funnel to separatethe organic layer. After washing with a saturated salt solution twotimes, it was dried with magnesium sulfate to obtain 237 g (95%) ofcrude 1,1,1,2,3,3-hexachloropropene.

EXAMPLE 12

285.5 g (1.0 mol) of 1,1,1,2,2,3,3-heptachloropropane and 0.3 g (0.1mmol) of tricaprylmethyl ammonium chloride were supplied to a roundbottom flask of 500 ml with a Dimroth condenser and a dropping funnel.

With keeping it at 40° C. and agitating violently, 250 ml of KOH aqueoussolution of 20% concentration was dropped for 1 hour. After the droppingwas finished, the reaction was carried out for 1 hour. Then, theagitating was stopped and a lower organic layer was analyzed.1,1,1,2,2,3,3-heptachloropropane as a raw material disappeared and theorganic layer consisted of only 1,1,1,2,3,3-hexachloropropene.

The reaction solution was transferred to a separatory funnel to separatethe organic layer. After washing with a saturated salt solution twotimes, it was dried with magnesium sulfate to obtain 232 g (93%) ofcrude 1,1,1,2,3,3-hexachloropropene.

EXAMPLE 13

285.5 g (1.0 mol) of 1,1,1,2,2,3,3-heptachloropropane and 0.3 g (0.1mmol) of tetrabutyl phosphonium chloride were charged into a roundbottom flask of 500 ml with a Dimroth condenser and a dropping funnel.

With keeping it at 40° C. and agitating violently, 250 ml of KOH aqueoussolution of 20% concentration was dropped for 1 hour. After the droppingwas finished, the agitating was stopped and a lower organic layer wasanalyzed. 1,1,1,2,2,3,3-heptachloropropane as a raw material disappearedand the organic layer consisted of only 1,1,1,2,3,3-hexachloropropene.

The reaction solution was transferred to a separatory funnel to separatethe organic layer. After washing with a saturated salt solution twotimes, it was dried with magnesium sulfate to obtain 239 g (96%) ofcrude 1,1,1,2,3,3-hexachloropropene.

EXAMPLE 14

285.5 g (1.0 mol) of 1,1,1,2,2,3,3-heptachloropropane and 0.3 g (0.1mmol) of trioctylmethyl ammonium chloride were charged into a roundbottom flask of 500 ml with a Dimroth condenser and a dropping funnel.

With keeping it at 40° C. and agitating violently, 250 ml of KOH aqueoussolution of 20% concentration was dropped for 1 hour. After the droppingwas finished, a reaction was advanced for 2 hours. Then the agitatingwas stopped and a lower organic layer was analyzed.1,1,1,2,2,3,3-heptachloropropane as a raw material disappeared and theorganic layer consisted of only 1,1,1,2,3,3-hexachloropropene.

The reaction solution was transferred to a separatory funnel to separatethe organic layer. After washing with a saturated salt solution twotimes, it was dried with magnesium sulfate to obtain 237 g (95%) ofcrude 1,1,1,2,3,3-hexachloropropene.

COMPARATIVE EXAMPLE 1

285.5 g (1.0 mol) of 1,1,1,2,2,3,3-heptachloropropane was charged into around bottom flask of 500 ml with a Dimroth condenser and a droppingfunnel.

With keeping it at 40° C. and agitating violently, 250 ml of KOH aqueoussolution of 20% concentration was dropped for 1 hour. After the droppingwas finished, a reaction was carried out for 3 hours. Then, theagitating was stopped and a lower organic layer was analyzed.

The reaction was carried out only a little, 63% of the organic layerconsisted of 1,1,1,2,2,3,3-heptachloropropane as a raw material, and theconversion ratio was 37%.

According to the above-mentioned results, 1,1,1,2,3,3-hexachloropropenecan be easily produced by the reaction based on the fourth invention.

EXAMPLE 15

By reacting under the same condition as that of Example 11 except forthe alkali aqueous solution used therein 20% KOH aqueous solution waschanged with 20% NaOH aqueous solution, 232 g (93%) of crude1,1,1,2,3,3-hexachloropropene was obtained.

EXAMPLE 16

A reaction was carried out under the same condition as that of Example 7except charging 29.9 g (0.1 mol) of SbCl₅ and 22.9 g (0.1 mol) of SbCl₃into a Hastelloy-made autoclave of 500 ml with a condenser.

As a product, 194 g of organic substance was obtained. It was confirmedwith GLC that 98% of the product was the objective1,1,1,3,3-pentafluroro-2,3-dichloropropane (93% of the yield). A mainby-product was 1,1,1-tetrafluoro-2,3,3-trichloropropane and a compoundadded by chlorine was not detected.

What is claimed is:
 1. A method of producing a1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane which comprisescontinuously reacting, at a contant pressure and in the liquid phase, acompound of the formula ##STR2## wherein X and Y are each Cl or F, withexcess hydrogen fluoride in the presence of at least one of an antimonytrihalogenide and an antimony pentahalogenide, while selectivelyremoving the 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane as it isformed.
 2. A method according to claim 1, wherein X and Y are Cl, andthe 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane is1,1,1,3,3-pentafluoro-2,3-dichloropropane.
 3. A method of producing1,1,1,3,3-pentafluoro-2,-3-dichloropropane which comprises reacting1,1,1,2,2,3,3-heptachloropropane with an alkali metal hydroxide in thepresence of a phase transfer catalyst to form1,1,1,2,3,3-hexachloropropene; and continuously reacting, at a constantpressure and in the liquid phase, 1,1,1,2,3,3-hexachloropropene withexcess hydrogen fluoride in the presence of at least one of an antimonytrihalogenide and an antimony pentahalogenide, while selectivelyremoving the 1,1,1,3,3-pentafluoro-2,3-dichlorochloropropane as it isformed.
 4. A method according to claim 3, wherein the transfer phasecatalyst is a tetraalkyl ammonium salt.
 5. A method according to claim3, wherein the phase transfer catalyst is a tetraalkylphosphonium salt.